Phenyl-azo-(polycyclic)heterocyclic metal complexes

ABSTRACT

A Polycyclic metal complexe of the formula WHEREIN A1 denotes a 2-3-membered lower alkylene radical, a 1,2lower-cycloalkylene, a 1,2-phenylene or 1,8-naphthylene radical, A2 denotes a 2-3-membered lower alkylene radical, a 1,2-lowercycloalkylene or 1,8-naphthylene radical, Me denotes a divalent metal atom, R1 and R3 denote hydrogen atoms or lower alkyl radicals, R2 denotes a hydrogen or halogen atom or a lower alkyl, aryl, nitro, nitrile or arylazo group, or the radicals R2 and R3 form a fused five to six- membered alicyclic ring, and in the case that R1 and R3 denote lower alkyl radicals R2 must not be hydrogen, are useful for coloring polymers in red-brown shades.

United States Patent n91 LEplattenier et al.

[ May 6,1975

[ PHENYL-AZO-(POLYCYCLIC)HETEROCY- CLlC METAL COMPLEXES [75] Inventors: Francois LEplattenier, Therwil;

Andre Pugin, Riehen, both of Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Dec. I2, 1972 [2]] Appl. No.: 314,493

[30] Foreign Application Priority Data Dec. 15, l97l Switzerland l8357/7l [52] US. Cl 260/146 R; 260/3l.8 R; 260/42.2l; 260M249; 260/145 C; 260/l48; 260/239 BC; 260/429 C; 2450/4299; 260/438.I;

[5 I} Int. Cl C09b 45/48 [58] Field of Search 260/l45 C, 146 R [56] References Cited FOREIGN PATENTS OR APPLICATIONS 369,837 7/l963 Switzerland 260/[46 R OTHER PUBLICATIONS Dimroth et al., 5.14-Dihydro-Dibenzo[b- .i][5.9.l4.l8]tetraaza [I4]Annulen, Ein Makrocyclischer Chelat Bildner, Annalen, 7l7, l37l47, 1968.

Primary Examiner-Floyd D. Higel Assistant ExaminerC. F. Warren Attorney, Agent, or FirmVincent J. Cavalieri [57] ABSTRACT A Polycyclic metal complexe of the formula wherein A denotes a 2 3-membered lower alkylene radical, a l,2-lower'cycloalkylene, a l,2-phenylene or 1,8-naphthylene radical, A denotes a 2-3-membered lower alkylene radical, a l,2-lower-cycloalkylene or 8 Claims, N0 Drawings 1 PHENYL-AZ()-( POLYCYCLIC )HETEROCYCLIC METAL COMPLEXES It has been found that coloured polycyclic metal complexes of the formula lE-R wherein A, denotes a 2-3-membered alkylene radical, a l,2-cycloalkylene, a l,2-phenylene or L8- naphthylene radical, A denotes a 2-3-membered alkylene radical, a 1,2-cycloalkylene or l,8-naphthylene radical, Me denotes a divalent metal atom, R and R denote hydrogen atoms or alkyl radicals, R denotes a hydrogen or halogen atom or an alkyl, aryl, nitro, nitrile or arylazo group, or the radicals R and R form a fused alicyclic ring, and in the case that R and R denote alkyl radicals R must not be hydrogen, are obtained if a tricyclic compound of the formula I2 II R c c R n l N A Me \9 R C C R is condensed with an alkylenediamine of which the amino groups are separated from one another by 2 3 carbon atoms, a l,2-cycloalkylenediamine, a 1,2- phenylenediamine or a l,8-naphthylenediamine.

The alkylene radicals represented by the symbols A and A are 2-3-membered, that is to say the amino groups can be separated from one another by 2 3 carbon atoms. They can be substituted by lower alkyl or alkoxy groups or halogen atoms and preferably contain 2 6 carbon atoms. If the radicals R R or R denote alkyl radicals, the latter can additionally contain substituents, for example halogen atoms. The radical R can also denote an aryl group, especially a phenyl group, which can optionally be substituted by halogen atoms or lower alkyl or alkoxy groups.

Compounds of particular interest are those of the formula III wherein A and A and Me have the indicated meaning, and X and y are hydrogen or halogen atoms, nitro, nitrile, lower alkyl or alkoxy groups, phenoxy groups are phenylazo groups which can be substituted by halogen atoms, lower alkyl or alkoxy groups in the phenyl radical, carbonamides, acyl groups, especially lower alkanoyl groups, acylamino groups, for example benzoylamino or lower alkanoylamino groups, lower alkoxycarbonyl or alkylsulphonyl groups, carboxylic acid or sulphonic acid groups or phenylazo groups which can be substituted by halogen atoms or nitro or lower alkyl groups.

Amongst the compounds of the formula II] there should especially be mentioned those of the formula i Y1 liil \FH N cs Me (ca N N at (in wherein Me, X, and Y, have the indicated meaning and m and n denote 2 or 3, and those of the formula uc on x (cl-1 Me \N/ g x Y Hi: CH

wherein Me, X Y, and n have the indicated meaning and X and Y are hydrogen or halogen atoms, lower alkyl, alkoxy, alkylsulphonyl or alkoxycarbonyl groups, phenyl or phenoxy groups which can be substituted by halogen atoms or lower alkyl or alkoxy groups in the phenyl radical, acylamino groups or carbonamido groups of which the amino groups can be substituted by lower alkyl groups or phenyl radicals which are optionally substituted by halogen atoms, lower alkyl or alkoxy groups or trifluoromethyl groups.

As the complex-forming divalent metal the compounds mentioned preferably contain zinc, cobalt and especially nickel and copper. However, nickel is very particularly preferred.

The starting substances preferentially used are tricyclic compounds of the formula wherein A Me, X and Y have the indicated meaning, and especially those of the formula wherein X Y Me and n have the indicated meaning.

The alkylenediamines preferably used are those of the formula wherein m denotes the number 2 4.

The following alkylenediamines may be mentioned as examples: ethylenediamine, 1,2-diaminopropane, l,3-

diaminopropane, 1,2-diaminobutane, 1,3- diaminobutane, 2,3-diaminobutane and l ,3- diaminopentane.

1,2-Diaminocyclohexane may be mentioned as an example of a cycloalkylenediamine.

As l,2-phenylenediamines there should especially be mentioned those of the formula wherein X and Y have the indicated meaning.

The tricyclic compounds of the formula ll are in part known. They are appropriately obtained by condensation of a diamine of the formula with a 1,3-dicarbonyl compound of the formula R COCHCOR for example malondialdehyde or especially a phenylazomalondialdehyde in the presence of salts of divalent metals, in a hydrophilic organic solvent.

When manufacturing symmetrical compounds of the formula I, isolation of the tricyclic compound of the formula [I can in certain cases be dispensed with, and the tetracyclic compound of the formula I can be obtained directly by condensation of equimolar amounts of 1,3-dicarbonyl compound and diamine in the presence of a divalent metal ion.

However, it proves desirable to isolate the compound of the formula 11 before the reaction with the diamine H NA NH The reaction of the compound of the formula II with the diamine H N-A -NH is appropriately carried out with a hydrophilic organic solvent, for example a lower aliphatic alcohol or especially in a lower fatty acid, in particular acetic acid, at temperatures of between 50 and 120C, preferably between 60 and 90C. In the reaction with aliphatic diamines, an excess of diamine can also be used as the solvent.

Because of their insolubility in the reaction medium, the metal complexes obtained can easily be isolated by filtering them off. They are valuable and particularly strongly coloured dyestuffs which can be used for dyeing the most diverse materials. The compounds which are free of acid groups which confer solubility in water are in particular suitable for pigmenting high molecular organic material, for example cellulose ethers and cellulose esters, such as ethylcellulose, acetylcellulose or nitrocellulose, polyamides, polyurethanes or polyesters, natural resins or synthetic resins, for example aminoplasts, especially urea-formaldehyde and melamineformaldehyde resins, alkyd resins, phenoplasts, polycarbonates, polyolefines, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, polyacrylic acid esters, rubber, casein, silicone and silicone resins, individually or as mixtures. It does not matter whether the abovementioned high molecular compounds are in the form of plastic masses or melts or in the form of spinning solutions, lacquers, paints or printing inks. Depending on the end use it proves advantageous to use the new pigments as toners or in the form of preparations. As a rule, the new pigments are distinguished by their general fastness properties and their colour strength.

Those of the compounds obtained according to the invention which contain sulphonic acid groups can be converted, by reaction with water-soluble calcium or barium salts, into the insoluble calcium or barium lakes, which are also outstandingly suitable for use as pigments.

1n the examples which follow the parts, unless otherwise stated, denote parts by weight and the percentages denote percentages by weight.

EXAMPLE 1 3.52 g 0.02 mol) of phenylazomalondialdehyde are added at C to a solution of 2.49 g (0.01 mol) of Ni(CH COO) 4 H 0 and 1.20 g (0.02 mol) of ethylenediamine in 50 ml of alcohol. The reaction mixture is heated under reflux after 3 hours. After cooling to 20C, the residue is filtered off and washed with water, alcohol and a little acetone. The compound of the formula l u% an CH 2 N\ /N cu I A l CH Hg Il- H2 CH i u N- which dyes polyvinyl chloride in red shades is obtained.

EXAMPLE 2 n 0 nil in are obtained.

5.0 g (0.0115 mol) of the tricyclic compound obtained according to paragraph 1 are dissolved in 100 ml of ethylenediamine and the solution is heated under reflux for 2 hours. The deep red solution is cooled to 20C. The crystals which have separated out are filtered off and washed with alcohol. 4.5 g of theory) of the red dyestuff of the formula 7 N 1 1 P C H CH N CH l 1 CH N \l CH l HC iili which dyes polyvinylchloride in red shades are 0b 20 tained.

EXAMPLE 3 4.33 g (0.01 mol) of the tricyclic compound obtained according to Example 2, paragraph 2 and 1.30 g (0.012 mol) of o-phenylenediamine in 50 ml of glacial acetic acid are heated under reflux for minutes. After cooling to C, the precipitate is filtered off and successively washed with glacial acetic acid, alcohol and acetone. 3.1 g (62% of theory) of the tetracyclic dyestuff of the formula which dyes polyvinylchloride in red-brown shades are obtained.

EXAMPLE 4 are obtained.

6.8 g (0.044 mol) of 1,8-diaminonaphthalene are added to a solution of 8.2 g (0.014 mol) of the tricyclic compound obtained according to paragraph I, in 150 ml of methylcellosolve. The reaction mixture is kept at between 1 [0 and C for 24 hours. After cooling to 20C. it is filtered and the filter residue is well washed with methylcellosolve, alcohol and acetone. A blackbrown dyestutf of the indicated formula is obtained.

The table which follows lists further symmetrical tetracyclic metal complexes of the initially mentioned formula l which are obtained if. following the instruction of the preceding examples, a dicarbonyl compound of the formula RKOCH UORi wherein the substituents R R and R have the meaning indicated in the columns 2 4. is reacted with the l ,Z-diamine mentioned in column 5 and the acetate of the metal mentioned in column 1, with isolation of the tricyclic compound of the formula ll. The dyestuffs obtained dye polyvinyl chloride in red-brown shades.

l 2 3 4 5 Me R R, R Diamine 5 Ni H p- Methylphenylazo H Ethylenediamine 6 Ni H p-Chlorophenylazo H Ethylenediamine 7 Ni H mAcetylamino- H Ethylenediamine phenylazo 8 Ni H p-Acetylamino- H Ethylenediamine phenylazo 9 Ni H o-Sulphophenyl- H Ethylenediamine azo H) Ni H Phenylazo H l .Z-Propylenediamine l 1 Ni H p-Chlorophenylazo H LZ-Propylenediamine l 2 Ni H Phenylazo H l,3-Propylenediarnine 13 Ni H p-Chlorophenylazo H l ,3-Propylenediamine 14 Ni H pCyanophenyla7o H LS-Propylenediamine l 5 Ni H p-Acetylamino- H l ,3-Propylenediamine phenylazo 16 Cu H Phenylazo H LZ-Ethylenediamine l 7 Cu H p-hlorophenylazo H l .2-Ethylenediamine I 8 Cu H Phenylazo H l ,2- Propylenediamine l9 Cu H Phenylazo H l ,3-Propylenediamine 20 Cu H p-Cyanophenylazo H l ,3Propylenediamine 2 l Cu H p-Acetylamind H l .3-Propylenediamine phenylazo 2 2 Ni H Phenylazo H 1.8-Naphtylenediamine 23 Ni H p-Chlorophenylazo H l ,S-Naphtylenediamine 24 Ni H p-Nitrophenyla1o H 1.8Naphtylenediamine 25 Ni H p-Cyanophenylazo H l .8-Naphylenediamine The table which follows lists asymmetrical tetracyclic wherein A is alkylene of two to three carbon atoms, l,2-lower-cycloalkylene, l,2-phenylene, or 1.8- naphthalene; A is a lower alkylene of two to three carbon atoms, 1,2-lower-cycloalkylene, or [,8- naphthalene; Me is Zn, Cu, Co or Ni; X and Y, is hydrogen, chloro, lower alkyl, lower alkoxy, phenoxy, phenylazo, lower alkanoyl, lower alkanoylamino, carbonamido, lower alkoxycarbonyl, trifluoromethyl, nitro, cyano, lower alkylsulphonyl, carboxylic acid group or sulphonic acid group.

2. A polycyclic metal complex of the formula compounds of the initially mentioned formula I which are obtained if. following the instructions of the pre- X ceding examples, 2 mols of a dicarbonyl compound of the formula =N' Y 1 R ac ca 2 i R GOSH-COR X 4 (CH n Me\ O wherein the substituents R R and R have the mean- I ing indicated in column 2 4, are reacted with 1 mol Hc C of the diamine mentioned in column 6 and the acetate of the metal listed in column 1 to give the tricyclic com- C pound of the formula ll, and the latter is reacted with fq= mol of the diamine mentioned in column 5.

Mixed tetracyclic complexes Diamine Diamine Me R, R R H,N-A,NH H NA NH 26 Ni H Phenylazo H o-Phenylenediamine Ethylenediamine 27 Ni H Phenylazo H 1,3-Propylenediamine Ethylenediamine 23 Ni H pCyanophenylazo H l,3-Propylenediamine Ethylenediamine 29 Cu H Phenylam H l.3-Propylenediamine Ethylenediamine 30 Ni H Phenylam H oPhenylenediumine l 3-Propylenediamine H (u H Phenylazo H oPhenylenediamine l.3-Propylenediamine EXAMPLE 32 65 parts of stabilised polyvinyl chloride, 35 parts of dioctyl phthalate and 0.2 part of the dyestuff obtained according to Example 1 are stirred together and then milled on a two-roll calender for 7 minutes at 140C. A film which is coloured red-brown is obtained.

We claim:

1. A polycyclic metal complex of the formula 3. The polycyclic metal complex according to claim 7. The polycyclic metal complex of claim I of the forl, of the formula mula 1 5 N N N N l Y I 1 C 11% CH m 11 \')H N N CH 2 (CH n/ Me (CH m til EH H H c x wherein X and Y have the meaning indicated in claim 1 d m d n d m 2 or 3 M i C Ni C or Z 8. The polycyclic metal complex ofclaim l of the for- 4. The polycyclic metal complex of claim 1 wherein mula Me denotes a divalent copper or nickel atom.

5. The polycyclic metal complex of claim 1 wherein Me denotes a divalent nickel atom. N N NHCOCH 6. The polycyclic metal complex of claim 1 of the for I j mula C 110 Cll 

1. A POLYCYCLIC METAL COMPLEX OF THE FORMULA
 2. A POLYCYCLIC METAL COPLEX OF THE FORMULA
 3. The polycyclic metal complex according to claim 1, of the formula
 4. The polycyclic metal complex of claim 1 wherein Me denotes a divalent copper or nickel atom.
 5. The polycyclic metal complex of claim 1 wherein Me denotes a divalent nickel atom.
 6. The polycyclic metal complex of claim 1 of the formula
 7. The polycyclic metal complex of claim 1 of the formula
 8. The polycyclic metal complex of claim 1 of the formula 